WO2020184569A1

WO2020184569A1 - Circuit board and method for producing circuit board

Info

Publication number: WO2020184569A1
Application number: PCT/JP2020/010342
Authority: WO
Inventors: 文起深津; 聡蜂屋
Original assignee: 出光興産株式会社
Priority date: 2019-03-12
Filing date: 2020-03-10
Publication date: 2020-09-17
Also published as: US20220192033A1; CN113557321A; JPWO2020184569A1

Abstract

A circuit board which sequentially comprises a resin base material 1 that has a dielectric loss tangent of 0.015 or less, a polyaniline layer 2 that contains a substituted or unsubstituted polyaniline, and a metal layer 3 in this order, said components being stacked with each other, and which is configured such that the polyaniline layer 2-side surface of the metal layer 3 has a surface roughness Rz_JIS of 0.5 μm or less.

Description

Circuit board and manufacturing method of circuit board

The present invention relates to a circuit board and a method for manufacturing a circuit board.

In recent years, the use of high-frequency electric signals has become active in a wide range of fields including, for example, in-vehicle radars and next-generation mobile phones, and circuit boards suitable for transmitting high-frequency electric signals are required.
As a conventional circuit board, for example, as disclosed in Patent Document 1, a substrate and a metal layer (copper foil or the like) bonded together with an adhesive or the like are used.

Japanese Unexamined Patent Publication No. 5-226831

When a base material and a metal layer are bonded together with an adhesive as in the conventional case, the metal surface is usually roughened by etching or the like to give unevenness (for example, surface roughness Rz _JIS 1 μm or more). , A method of ensuring adhesion is adopted by the anchor effect. Resin substrates with low dielectric loss tangent are suitable for circuit boards for high-frequency electrical signals, but resin substrates with low dielectric loss tangent have low adhesion to adhesives, so it is necessary to strengthen the anchor effect by roughening the metal surface. The sex becomes greater.

On the other hand, the higher the frequency of the electric signal, the more the current is concentrated on the conductor surface (skin effect), so that the transmission distance of the high-frequency electric signal becomes longer in the roughened metal, and the transmission loss and delay increase. growing. Therefore, it is desired that the metal surface of the circuit board for high-frequency electric signals is smooth, but it is difficult to improve the smoothness in view of the adhesion.

An object of the present invention is to provide a circuit board suitable for transmission of a high-frequency electric signal, and a method for manufacturing the circuit board.

As a result of diligent studies by the present inventors, an extremely smooth metal layer can be formed by electroless plating technology using polyaniline even if the resin substrate has a low dielectric loss tangent, and the obtained laminate (circuit board) adheres to each other. The present invention was completed by finding excellent properties.

According to the present invention, the following circuit boards and the like are provided.
1. 1. With a resin base material having a dielectric loss tangent of 0.015 or less,
A polyaniline layer containing substituted or unsubstituted polyaniline,
The metal layer and the metal layer are laminated in this order and included.
The surface roughness Rz _JIS of the surface on the polyaniline layer side of the metal layer is 0.5 μm or less.
Circuit board.
2. 2. The circuit board according to 1 above, wherein the surface roughness Rz _JIS of the surface of the metal layer on the polyaniline layer side is 0.25 μm or less.
3. 3. The circuit board according to 1 or 2 above, wherein the polyaniline layer has a thickness of 5 μm or less.
4. The circuit board according to any one of 1 to 3 above, wherein the resin substrate contains at least one selected from the group consisting of syndiotactic polystyrene, polyimide, liquid crystal polymer, polytetrafluoroethylene, and polyolefin.
5. The circuit board according to any one of 1 to 4, wherein the resin base material contains syndiotactic polystyrene.
6. The circuit board according to any one of 1 to 5, wherein the metal layer contains one or more metals selected from the group consisting of Cu, Ni, Au, Pd, Ag, Sn, Co and Pt.
7. The circuit board according to any one of 1 to 6, wherein the metal layer contains Cu.
8. The circuit board according to any one of 1 to 7, wherein the polyaniline layer contains substituted or unsubstituted polyaniline as a dopant-doped polyaniline composite.
9. The circuit board according to 8 above, wherein the dopant is an organic acid ion generated from a sulfosuccinic acid derivative represented by the following formula (III).

(In formula (III), M is a hydrogen atom, an organic radical or an inorganic radical. M'is a valence of M. R ¹³ and R ¹⁴ are independently hydrocarbon groups or-(, respectively. R ^¹⁵ _O) ^.R ¹⁵ is r ^{-R 16} radicals are each independently a hydrocarbon group or a silylene ^{group, R 16} is a hydrogen atom, a hydrocarbon group, or ^R ₁₇ 3 Si- groups, r is 1 These are the above integers. R ¹⁷ is an independent radical.)
10. 8. The circuit board according to 8 or 9, wherein the dopant is sodium di-2-ethylhexyl sulfosuccinate.
11. The circuit board according to any one of 1 to 10 above, which is used for transmitting a high frequency electric signal having a frequency of 1 GHz or more.
12. The method for manufacturing a circuit board according to any one of 1 to 11 above.
A step of applying one or more treatments selected from the group consisting of an active energy ray irradiation treatment, a corona treatment, and a frame treatment to the surface of the resin base material.
A step of forming the polyaniline layer on the surface of the resin base material subjected to the treatment, and
The step of supporting the electroless plating catalyst on the polyaniline layer and
A step of forming a metal layer by performing electroless plating on the polyaniline layer on which the electroless plating catalyst is supported is included.
How to manufacture a circuit board.
13. The method for manufacturing a circuit board according to the above 12, wherein the surface of the resin base material is subjected to an active energy ray irradiation treatment.
14. The method for manufacturing a circuit board according to the above 13, wherein the active energy ray is ultraviolet rays.
15. The method for manufacturing a circuit board according to the above 14, wherein the light source of the ultraviolet rays is a high-pressure mercury lamp or a metal halide lamp.
16. The method for producing a circuit board according to any one of 12 to 15, wherein the polyaniline layer is formed by a coating method using a composition containing a substituted or unsubstituted polyaniline.
17. 16. The method for producing a circuit board according to 16, wherein the composition comprises a substituted or unsubstituted polyaniline as a dopant-doped polyaniline composite.
18. The method for producing a circuit board according to 17 above, wherein the concentration of the polyaniline complex in the composition is 15% by mass or less.
19. The method for manufacturing a circuit board according to any one of 12 to 18, wherein the electroless plating catalyst is Pd.

According to the present invention, it is possible to provide a circuit board suitable for transmission of a high-frequency electric signal and a method for manufacturing the circuit board.

It is the schematic which shows the layer structure of the circuit board which concerns on one Embodiment of this invention.

Hereinafter, the circuit board and the like according to the embodiment of the present invention will be described.
In this specification, "x to y" represents a numerical range of "x or more and y or less".
Further, the term "component (X)" refers only to the compound corresponding to the component (X) in the reagent even when a commercially available reagent is used, and other components (solvent) in the reagent. Etc.) are not included.
Further, the preferred provisions can be arbitrarily adopted. That is, one preferred provision can be adopted in combination with one or more other preferred provisions. It can be said that the combination of preferable ones is more preferable.

[Circuit board]
FIG. 1 is a schematic view showing a layer structure of a circuit board according to an embodiment of the present invention.
In the circuit board according to the embodiment of the present invention, the resin base material 1 having a dielectric loss tangent of 0.015 or less, the polyaniline layer 2 containing substituted or unsubstituted polyaniline, and the metal layer 3 are laminated in this order. The surface roughness Rz _JIS of the surface of the metal layer 3 on the polyaniline layer 2 side is 0.5 μm or less.
Hereinafter, each layer constituting the circuit board according to the embodiment of the present invention will be described.

[Resin base material]
In one embodiment, the resin substrate has a dielectric loss tangent of 0.015 or less.
The resin used for the resin base material is not particularly limited, and includes, for example, a group consisting of syndiotactic polystyrene, liquid crystal polymer, polytetrafluoroethylene, polyolefin (for example, polyethylene or polypropylene including modified polyolefin), polyphenylene sulfide, polyamide and the like. It can include one or more selected species.
In one embodiment, the resin substrate preferably has a low dielectric loss tangent, preferably 0.015 or less, preferably 0.01 or less, and more preferably 0.005 or less. If the dielectric loss tangent of the resin base material is high, the attenuation tends to be large in the high frequency circuit.

The dielectric loss tangent is a value measured by the cavity resonator method (JIS R1641: 2007) at a measurement frequency of 10 GHz and a temperature of 25 ° C. using a measuring device (a network analyzer "E8631A" manufactured by Keysight Technology Co., Ltd.).

[Polyaniline layer]
(Polyaniline)
In one embodiment, the polyaniline layer comprises substituted or unsubstituted polyaniline.
The substituted or unsubstituted polyaniline may be used alone (in a state where the "polyaniline complex" described later is not formed), but as a polyaniline complex in which the substituted or unsubstituted polyaniline is doped with a dopant, polyaniline It is preferably contained in the layer.

The weight average molecular weight of polyaniline (hereinafter referred to as molecular weight) is preferably 20,000 or more. The molecular weight is preferably 20,000 to 500,000, more preferably 20,000 to 300,000, and even more preferably 20,000 to 200,000. The weight average molecular weight is not the molecular weight of the polyaniline complex, but the molecular weight of polyaniline.

The molecular weight distribution is preferably 1.5 or more and 10.0 or less. From the viewpoint of conductivity, a small molecular weight distribution is preferable, but from the viewpoint of solubility in a solvent, a wide molecular weight distribution may be preferable.
The molecular weight and the molecular weight distribution are measured by gel permeation chromatography (GPC) in terms of polystyrene.

Substituents of the substituted polyaniline include linear or branched hydrocarbon groups such as methyl group, ethyl group, hexyl group and octyl group; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; tri Examples thereof include halogenated hydrocarbons such as a fluoromethyl group (-CF ₃ groups).
As the polyaniline, unsubstituted polyaniline is preferable from the viewpoint of versatility and economy.

Substituted or unsubstituted polyaniline is preferably a polyaniline obtained by polymerization in the presence of an acid containing no chlorine atom. An acid containing no chlorine atom is, for example, an acid composed of atoms belonging to groups 1 to 16 and 18. Specific examples include phosphoric acid. Examples of the polyaniline obtained by polymerizing in the presence of an acid containing no chlorine atom include polyaniline obtained by polymerizing in the presence of phosphoric acid.
The polyaniline obtained in the presence of a chlorine atom-free acid can lower the chlorine content of the polyaniline complex.

Examples of the dopant of the polyaniline complex include Bronsted acid or Bronsted acid ion generated from a salt of Bronsted acid, preferably an organic acid ion generated from an organic acid or a salt of an organic acid, and more preferably the following formula. It is an organic acid ion generated from the compound (proton donor) represented by (I).
In the present invention, the dopant may be expressed as a specific acid or the dopant may be expressed as a specific salt, both of which the specific acid ion generated from the specific acid or the specific salt is described above. It is assumed that the π-conjugated polymer is doped.

M (XARn) m (I)
M of the formula (I) is a hydrogen atom, an organic radical or an inorganic radical.
Examples of the organic free group include a pyridinium group, an imidazolium group, an anilinium group and the like. Examples of the inorganic free radical include lithium, sodium, potassium, cesium, ammonium, calcium, magnesium, iron and the like.
X is the Formula (I), anionic groups, such as -SO ₃ ^- group, _-PO ^{3 _2-group,} -PO 2 (OH) ^- group, -OPO ₃ ^2-group, -OPO ₂ (OH) ^- Groups, -COO ^- groups and the like can be mentioned, preferably -SO ₃ ^- groups.

A of the formula (I) is a substituted or unsubstituted hydrocarbon group (for example, 1 to 20 carbon atoms).
Hydrocarbon groups are chain or cyclic saturated aliphatic hydrocarbon groups, chain or cyclic unsaturated aliphatic hydrocarbon groups, or aromatic hydrocarbon groups.
Examples of the chain saturated aliphatic hydrocarbon group include a linear or branched alkyl group (for example, 1 to 20 carbon atoms). Examples of the cyclic saturated aliphatic hydrocarbon group include cycloalkyl groups (for example, 3 to 20 carbon atoms) such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group. The cyclic saturated aliphatic hydrocarbon group may be a condensation of a plurality of cyclic saturated aliphatic hydrocarbon groups. For example, a norbornyl group, an adamantyl group, a condensed adamantyl group and the like can be mentioned. Examples of the chain unsaturated aliphatic hydrocarbon (having 2 to 20 carbon atoms, for example) include a linear or branched alkenyl group. Examples of the cyclic unsaturated aliphatic hydrocarbon group (for example, 3 to 20 carbon atoms) include a cyclic alkenyl group. Examples of the aromatic hydrocarbon group (for example, 6 to 20 carbon atoms) include a phenyl group, a naphthyl group, an anthracenyl group and the like.

When A is a substituted hydrocarbon group, the substituents are an alkyl group (for example, 1 to 20 carbon atoms), a cycloalkyl group (for example, 3 to 20 carbon atoms), a vinyl group, an allyl group, and an aryl group (carbon). The number is, for example, 6 to 20), an alkoxy group (for example, 1 to 20 carbon atoms), a halogen atom, a hydroxy group, an amino group, an imino group, a nitro group, a silyl group, or an ester bond-containing group.

R in formula (I) is bound to A and is -H, -R ¹ , -OR ¹ , -COR ¹ , -COOR ¹ ,-(C = O)-(COR ¹ ), or-(C). = O)-There is a substituent represented by (COOR ¹ ), and R ¹ is a hydrocarbon group, a silyl group, an alkylsilyl group,-(R ² O) x-R ³ groups, or-which may contain a substituent. a ^{_{(OSiR 3 2) x-OR}} 3 group. R ² is an alkylene group, R ³ is a hydrocarbon group, and x is an integer of 1 or more. If x is 2 or more, plural R ² may be the same or different, or different in each of a plurality of R ³ are the same.

The hydrocarbon group of R ¹ (for example, 1 to 20 carbon atoms) includes a methyl group, an ethyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group and a pentadecyl group. , Eikosanyl group and the like. The hydrocarbon group may be linear or branched.
Substituents of the hydrocarbon group are an alkyl group (for example, 1 to 20 carbon atoms), a cycloalkyl group (for example, 3 to 20 carbon atoms), a vinyl group, an allyl group, and an aryl group (for example, 6 to 20 carbon atoms). , An alkoxy group (for example, 1 to 20 carbon atoms), a halogen group, a hydroxy group, an amino group, an imino group, a nitro group or an ester bond-containing group. The hydrocarbon group of R ³ is the same as that of R ¹ .

Alkylene group R ² (the number of carbon atoms, for example 1 to 20) include a methylene group, an ethylene group and a propylene group.
N in the formula (I) is an integer of 1 or more. When n is 2 or more, the plurality of Rs may be the same or different.
M in the formula (I) is a valence of M / a valence of X.

As the compound represented by the formula (I), a compound containing two or more dialkylbenzenesulphonic acid, dialkylnaphthalene sulfonic acid, or an ester bond is preferable.
As the compound containing two or more ester bonds, a sulfoftal acid ester or a compound represented by the following formula (II) is more preferable.

In formula (II), M and X are the same as in formula (I). X is, -SO ₃ ^- group.
R ^4, ^{R 5} and ^{R 6} are each independently a hydrogen atom, a hydrocarbon group, or ^R ₉ 3 Si- groups. Three R ⁹ are each independently a hydrocarbon group.
When R ⁴ , R ⁵ and R ⁶ are hydrocarbon groups, the hydrocarbon group includes a linear or branched alkyl group having 1 to 24 carbon atoms and an aryl group containing an aromatic ring (for example, 6 to 24 carbon atoms). 20), an alkylaryl group (for example, 7 to 20 carbon atoms) and the like can be mentioned.
The hydrocarbon group of R ⁹ is the same as that of R ⁴ , R ⁵ and R ⁶ .

R ⁷ and R ⁸ of the formula (II) are each independently a hydrocarbon group or-(R ¹⁰ O) _q- R ¹¹ groups. R ¹⁰ is a hydrocarbon group or a silylene ^{group, R 11} is a hydrogen atom, a Si- hydrocarbon radical or ^R ₁₂ 3, q is an integer of 1 or more. Three R ¹² are each independently a hydrocarbon group.

When R ⁷ and R ⁸ are hydrocarbon groups, the hydrocarbon group has 1 to 24 carbon atoms, preferably a linear or branched alkyl group having 4 or more carbon atoms, and an aryl group containing an aromatic ring (carbon number). Examples include 6 to 20), alkylaryl groups (for example, 7 to 20 carbon atoms), and specific examples thereof include linear or branched butyl groups, pentyl groups, hexyl groups, and octyl groups. Groups, decyl groups and the like can be mentioned.

In R ⁷ and R ⁸ , when R ¹⁰ is a hydrocarbon group, the hydrocarbon group includes, for example, a linear or branched alkylene group having 1 to 24 carbon atoms, or an arylene group containing an aromatic ring (for example, the number of carbon atoms is, for example). 6 to 20), an alkylarylene group (for example, 7 to 20 carbon atoms), or an arylalkylene group (for example, 7 to 20 carbon atoms). Further, in R ⁷ and R ⁸ , when R ¹¹ and R ¹² are hydrocarbon groups, the hydrocarbon groups are the same as in the case of R ⁴ , R ⁵ and R ⁶ , and q is 1 to 10. It is preferable to have.

Specific examples of the compound represented by the formula (II) when R ⁷ and R ⁸ are − (R ¹⁰ O) _{q −} R ¹¹ groups are two compounds represented by the following formula.

(In the formula, X is the same as the formula (I).)

The compound represented by the above formula (II) is more preferably a sulfosuccinic acid derivative represented by the following formula (III).

In formula (III), M is similar to formula (I). m'is the valence of M.
R ¹³ and R ¹⁴ are each independently a hydrocarbon group or-(R ¹⁵ O) _r- R ¹⁶ groups. R ¹⁵ is a hydrocarbon group or a silylene ^{group, R 16} is a hydrogen atom, a hydrocarbon group, or ^R ₁₇ 3 Si- groups, r is an integer of 1 or more. Each of the three R ^17s is an independent hydrocarbon group. When r is 2 or more, the plurality of R ^15s may be the same or different.

When R ¹³ and R ¹⁴ are hydrocarbon groups, the hydrocarbon groups are the same as those of R ⁷ and R ⁸ .
In R ¹³ and R ¹⁴ , the hydrocarbon group when R ¹⁵ is a hydrocarbon group is the same as that of R ¹⁰ described above. Further, in R ¹³ and R ¹⁴ , when R ¹⁶ and R ¹⁷ are hydrocarbon groups, the hydrocarbon groups are the same as those of R ⁴ , R ⁵ and R ⁶ described above.
r is preferably 1 to 10.

Specific examples of the case where R ¹³ and R ¹⁴ are − (R ¹⁵ O) _{r −} R ¹⁶ groups are the same as those of − (R ¹⁰ O) _{q −} R ¹¹ in R ⁷ and R ⁸ .
The hydrocarbon groups of R ¹³ and R ¹⁴ are the same as those of R ⁷ and R ⁸ , and butyl group, hexyl group, 2-ethylhexyl group and decyl group are preferable.

As the compound represented by the formula (I), di-2-ethylhexyl sulfosuccinic acid and sodium di-2-ethylhexyl sulfosuccinate (aerosol OT) are preferable.

The fact that the dopant of the polyaniline complex is doped with substituted or unsubstituted polyaniline can be confirmed by ultraviolet / visible / near-infrared spectroscopy or X-ray photoelectron spectroscopy, and the dopant carries carriers in polyaniline. As long as it has sufficient acidity to generate it, it can be used without any particular restrictions on its chemical structure.

The doping ratio of the dopant to polyaniline is preferably 0.35 or more and 0.65 or less, more preferably 0.42 or more and 0.60 or less, still more preferably 0.43 or more and 0.57 or less, and particularly. It is preferably 0.44 or more and 0.55 or less.
The doping rate is defined as (the number of moles of dopant doped in polyaniline) / (the number of moles of monomer unit of polyaniline). For example, a polyaniline complex containing an unsubstituted polyaniline and a dopant having a doping ratio of 0.5 means that one dopant is doped with respect to two monomer unit molecules of polyaniline.

The doping rate can be calculated if the number of moles of the dopant and the polyaniline monomer unit in the polyaniline complex can be measured. For example, when the dopant is an organic sulfonic acid, the number of moles of sulfur atoms derived from the dopant and the number of moles of nitrogen atoms derived from the monomer unit of polyaniline are quantified by an organic elemental analysis method, and the ratio of these values is taken. The doping rate can be calculated. However, the method for calculating the dope rate is not limited to the means.

The polyaniline complex may or may not further contain phosphorus.
When the polyaniline complex contains phosphorus, the phosphorus content is, for example, 10 mass ppm or more and 5000 mass ppm or less.
The phosphorus content can be measured by ICP emission spectroscopy.
Further, the polyaniline complex preferably does not contain a Group 12 element (for example, zinc) as an impurity.

The polyaniline complex can be produced by a well-known production method. For example, it can be produced by chemically oxidizing and polymerizing substituted or unsubstituted aniline in a solution containing a proton donor, phosphoric acid, and an emulsifier different from the proton donor and having two liquid phases. It can also be produced by adding an oxidative polymerization agent to a solution containing a substituted or unsubstituted aniline, a proton donor, a phosphoric acid, and an emulsifier different from the proton donor and having two liquid phases.

Here, the "solution having two liquid phases" means a state in which two incompatible liquid phases are present in the solution. For example, it means a state in which a "high-polarity solvent phase" and a "low-polarity solvent phase" are present in the solution.
Further, the "solution having two liquid phases" also includes a state in which one liquid phase is a continuous phase and the other liquid phase is a dispersed phase. For example, the "high-polarity solvent phase" is a continuous phase and the "low-polarity solvent phase" is a dispersed phase, and the "low-polarity solvent phase" is a continuous phase and the "highly polar solvent phase" is a dispersed phase. The state that is is included.
Water is preferable as the highly polar solvent used in the method for producing the polyaniline complex, and aromatic hydrocarbons such as toluene and xylene are preferable as the low polar solvent.

The proton donor is preferably a compound represented by the above formula (I).

The above emulsifier can be either an ionic emulsifier whose hydrophilic portion is ionic and a nonionic emulsifier whose hydrophilic moiety is nonionic, and one or more emulsifiers are mixed. You may use it.

Oxidizing agents used in chemical oxidative polymerization include peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, and hydrogen peroxide; ammonium dichromate, ammonium perchlorate, iron (III) sulfate, iron trichloride. (III), manganese dioxide, iodic acid, potassium permanganate, iron paratoluenesulfonate and the like can be used, and persulfate such as ammonium persulfate is preferable.
These may be used alone or in combination of two or more.

(binder)
The polyaniline layer can contain a binder in addition to one or more selected from substituted or unsubstituted polyaniline and polyaniline complexes.
As the binder, for example, one or more selected from the group consisting of acrylic type, urethane type, epoxy type, polyamide type, vinyl type, polyvinyl acetal type, polyester type, polyester polyol type, polyether polyol type and polycarbonate type shall be contained. Can be done. Further, a polymer having an acidic group such as a carboxy group or a sulfoxy group in the structure (for example, urethane having a carboxyl group or polyester having a carboxyl group) is preferable.
Further, the polyaniline layer can also contain a binder having a monomer, oligomer or polymer having a reactive functional group such as acrylate or methacrylate at the end cured by ultraviolet rays, electron beams or the like.

(Other ingredients)
The polyaniline layer can contain polyaniline, a polyaniline complex, and other components other than the binder as long as the effects of the present invention are not impaired. Examples of other components include additives such as inorganic materials, curing agents, plasticizers, and organic conductive materials.

Inorganic materials are added for the purpose of improving, for example, strength, surface hardness, dimensional stability and other mechanical properties, or electrical properties such as conductivity. Specific examples of the inorganic material include silica (silicon dioxide), titania (titanium dioxide), alumina (aluminum oxide), Sn-containing In ₂ O ₃ (ITO), Zn-containing In ₂ O ₃ , and In ₂ O ₃ . Examples thereof include co-substituted compounds (oxides in which tetravalent elements and divalent elements are substituted with trivalent In), Sb-containing SnO ₂ (ATO), ZnO, Al-containing ZnO (AZO), Ga-containing ZnO (GZO), and the like. ..

The curing agent is added for the purpose of improving, for example, strength, surface hardness, dimensional stability and other mechanical properties. Specific examples of the curing agent include a thermosetting agent such as a phenol resin, and a photocuring agent using an acrylate-based monomer and a photopolymerizable initiator.

The plasticizer is added for the purpose of improving mechanical properties such as tensile strength and bending strength, for example. Specific examples of the plasticizer include phthalates and phosphoric acid esters.

Examples of the organic conductive material include carbon black and carbon materials such as carbon nanotubes.

The film thickness of the polyaniline layer is not particularly limited. In one embodiment, the film thickness of the polyaniline layer may be, for example, 0.1 μm or more, 0.5 μm or more, or 1 μm or more. The film thickness of the polyaniline layer may be, for example, 3 μm or less, 2 μm or less, 1 μm or less, or 0.5 μm or less.
By forming the polyaniline layer thinly, the thickness of the circuit board can be reduced. As a result, the circuit board can be made more compact and can be easily mounted in the mechanical device. Further, by forming the polyaniline layer thinly, the surface of the polyaniline layer can be smoothed, whereby the surface roughness Rz _JIS of the surface of the metal layer on the polyaniline layer side can be preferably 0.5 μm or less.

In one embodiment, for example, 70% by mass or more, 80% by mass or more, 90% by mass or more, 98% by mass or more, 99% by mass or more, 99.5% by mass or more, 99.9% by mass or more, or the polyaniline layer. 100% by mass
One or more selected from substituted or unsubstituted polyaniline and polyaniline complex,
One or more selected from substituted or unsubstituted polyaniline and polyaniline complex and binder, or one or more selected from substituted or unsubstituted polyaniline and polyaniline complex, binder and arbitrarily selected from the other components described above. It may be one or more kinds of components.
The resin composition according to one aspect of the present invention is
One or more selected from essentially substituted or unsubstituted polyanilines and polyaniline complexes,
One or more selected from essentially substituted or unsubstituted polyaniline and polyaniline complexes and binders, or one or more selected from essentially substituted or unsubstituted polyaniline and polyaniline complexes, binders and other components described above. It may consist of one or more components arbitrarily selected from.
In this case, unavoidable impurities may be contained.

In one embodiment, the content of the substituted or unsubstituted polyaniline in the polyaniline layer may be 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, or 25% by mass or more. When the content of the substituted or unsubstituted polyaniline in the polyaniline layer is 5% by mass or more, the precipitation property of the electroless plating is improved. The upper limit is not particularly limited, and may be, for example, 100% by mass or less, 90% by mass or less, 80% by mass, 70% by mass or less, 65% by mass or less, and the like. When the content of the substituted or unsubstituted polyaniline in the polyaniline layer is less than 100% by mass, for example, when it is as small as 90% by mass or less, 80% by mass, 70% by mass or less, and further 65% by mass or less. , Binder and the like can improve the adhesion and coating strength of the polyaniline layer. The content of the substituted or unsubstituted polyaniline referred to here is the total content of the substituted or unsubstituted polyaniline forming the polyaniline complex and the substituted or unsubstituted polyaniline not forming the polyaniline complex. Is.

[Metal layer]
The metal layer is a layer containing metal.
The metal is not particularly limited and may include, for example, one or more metals selected from the group consisting of Cu, Ni, Au, Pd, Ag, Sn, Co and Pt. In one embodiment, the metal layer comprises Cu.
The metal layer may be either a single layer body or a laminated body having two or more layers having different metal compositions.
In one embodiment, the surface roughness Rz _JIS of the surface of the metal layer on the polyaniline layer side is 0.5 μm or less, 0.45 μm or less, 0.40 μm or less, 0.35 μm or less, 0.3 μm or less, 0.25 μm or less. , 0.2 μm or less, 0.15 μm or less, 0.1 μm or less, 0.08 μm or less, 0.05 μm or less, or 0.02 μm or less. Since the surface roughness Rz _JIS is small, it is possible to further prevent the transmission loss of the high frequency electric signal. The lower limit of the surface roughness Rz _JIS is not particularly limited, and may be, for example, 0.005 μm or more, 0.007 μm or more, or 0.01 μm or more.
Surface roughness Rz _JIS is a ten-point average roughness measured in accordance with JIS B 0601 (2001).

When the metal layer is formed on the polyaniline layer by electroless plating, the surface roughness Rz _JIS measured for the surface of the polyaniline layer (the surface on which the metal layer is formed later) before being subjected to electroless plating is obtained. , The surface roughness of the surface of the metal layer on the polyaniline layer side is Rz _JIS .

The film thickness of the metal layer is not particularly limited. In one embodiment, the film thickness of the metal layer is, for example, 0.1 μm or more, 0.3 μm or more, 0.5 μm or more, 0.8 μm or more, 1 μm or more, 5 μm or more, 10 μm or more, 18 μm or more, or 30 μm or more. There may be. Further, the film thickness of the metal layer may be, for example, 500 μm or less, or 300 μm or less, 200 μm or less, 150 μm or less, 100 μm or less, or 50 μm or less.

[Use]
In one embodiment, the metal layer of the circuit board is used for transmitting electrical signals. According to the circuit board according to one embodiment, transmission loss can be prevented regardless of the frequency of the electric signal.

Further, in one embodiment, the metal layer is used for transmitting a high frequency electric signal having a frequency of 1 GHz or more. The high frequency electric signal has, for example, a frequency of 3 GHz or more, 4 GHz or more, 5 GHz or more, 7 GHz or more, 10 GHz or more, 15 GHz or more, 20 GHz or more, 25 GHz or more, 30 GHz or more, 50 GHz or more, 80 GHz or more, 100 GHz or more, or 110 GHz or more. There may be. The upper limit of such a frequency is not particularly limited, and may be, for example, 200 GHz or less. According to the circuit board according to the embodiment, transmission loss can be prevented even when such a high frequency electric signal is transmitted.

The form of the circuit board is not particularly limited, and is, for example, a printed wiring board (PWB; printed wiring board), a printed circuit board (PCB; printed circuit board), or a flexible printed circuit board (FPC; flexible printed circuit boards). May be good.

[Manufacturing method of circuit board]
The method for manufacturing a circuit board according to an embodiment of the present invention can be used for manufacturing the circuit board described above.

In one embodiment, the method of manufacturing a circuit board is
(A) A step of applying one or more treatments selected from the group consisting of active energy ray irradiation treatment, corona treatment, and frame treatment to the surface of the resin base material.
(B) A step of forming a polyaniline layer on the surface of the resin base material subjected to the above treatment, and
(C) A step of supporting an electroless plating catalyst on a polyaniline layer and
(D) The step of forming a metal layer by performing electroless plating on the polyaniline layer on which the electroless plating catalyst is supported is included.

[Step (A)]
In the step (A), the surface of the base material is subjected to one or more treatments selected from the group consisting of an active energy ray irradiation treatment, a corona treatment, and a frame treatment.
In the present specification, the "active energy ray" has an activity of modifying the surface of the base material, and it is possible to use a material capable of improving the adhesion between the base material and the polyaniline layer by such modification. it can. As a method for evaluating the improvement in adhesion, the method for evaluating "adhesion before plating" described in Examples is used. Examples of such active energy rays include ultraviolet rays, electron beams, X-rays and the like, and among these, ultraviolet rays are preferable. The ultraviolet rays are not particularly limited, and for example, ultraviolet rays using a high-pressure mercury lamp or a metal halide lamp as a light source can be used.

[Step (B)]
In step (B), a polyaniline layer is formed on the surface of a substrate that has been subjected to one or more treatments selected from the group consisting of active energy ray irradiation treatment, corona treatment, and frame treatment. The method for forming the polyaniline layer is not particularly limited, and for example, a coating method or the like can be used. The coating method is not particularly limited as long as it forms a polyaniline layer by applying a coating liquid, and various coating methods, printing methods, etc. can be applied, for example, bar coating, spin coating, knife coating, and blade. You can select from the group consisting of coat, squeeze coat, reverse roll coat, gravure roll coat, curtain coat, spray coat, die coat, dipping, comma coat, dispenser, pad printing, gravure printing, flexographic printing, and inkjet printing. In one embodiment, when the bar coating method is used as the coating method, the surface of the polyaniline layer can be further smoothed.

In one embodiment, the coating liquid used in the coating method can contain a substituted or unsubstituted polyaniline and a solvent. In this case, the polyaniline layer is formed by drying and removing the solvent.

The solvent is not particularly limited, for example, methanol, ethanol, isopropyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, diacetone alcohol, 3-methoxy-1-butanol, 3-methoxy-3-methyl-1-butanol, Ethyl carbitol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, solvent naphtha, tetrahydrofuran, diethyl ether, n-butyl acetate, n-butanol, propylene glycol monomethyl ether acetate, γ-butyrolactone, tetraline, 2-butoxy-2 -Ethanol, dipropylene glycol monopropyl ether, 1,3-dimethylimidazolidinone, N-methylpyrrolidone and the like can be mentioned. One of these may be used alone, or two or more thereof may be used in combination.
Further, instead of the above solvent, it is also possible to use it as a solvent-free system in which a monomer, oligomer or polymer curable by ultraviolet rays or electron beams is added to adjust the viscosity and liquid properties. The cured product of these monomers, oligomers or polymers can be included as a binder in the polyaniline layer.

In addition, the coating liquid can contain the components described as the components that can be contained in the polyaniline layer.

In one aspect, the coating (composition) comprises a substituted or unsubstituted polyaniline as the dopant-doped polyaniline complex described above. The concentration of the polyaniline complex in the composition can be, for example, 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, or 15% by mass or less. When the concentration of the polyaniline complex in the composition is as low as described above, the thixotropic property of the composition is lowered, the smoothness of the polyaniline layer to be coated is improved, and the polyaniline layer side in the metal layer is improved. The surface roughness Rz _JIS of the surface can be preferably 0.5 μm or less. The concentration of the polyaniline complex in the composition may be further 13% by mass or less, 10% by mass or less, 8% by mass or less, or 5% by mass or less. The lower limit of the concentration of the polyaniline complex in the composition is not particularly limited, and can be, for example, 1% by mass or more.

After forming the polyaniline layer, the degreasing step can be performed before forming the metal layer. In the degreasing step, the surface of the electroless plating base film is degreased and washed with a solvent such as a surfactant or alcohol to improve wettability. As the surfactant, anionic, cationic or nonionic surfactants can be appropriately used. When a cationic surfactant is used, it can be diluted to 1 to 3% by mass with, for example, ion-exchanged water. The dilution ratio can be appropriately adjusted depending on the type of surfactant, solvent, etc. used for degreasing cleaning.

[Step (C)]
In the step (C), the electroless plating catalyst is supported on the polyaniline layer. The step (C) can be carried out after forming the polyaniline layer, preferably after the degreasing step.

Examples of the electroless plating catalyst include Pd metal (catalyst metal) and the like. In order to support the electroless plating catalyst on the polyaniline layer, the polyaniline layer can be brought into contact with a solution containing the electroless plating catalyst.
When Pd is used as the electroless plating catalyst, when a Pd compound solution is brought into contact with the polyaniline, preferably the polyaniline complex, the Pd ion is adsorbed and the Pd ion is reduced to the Pd metal by its reducing action. The reduced Pd, that is, the Pd in the metallic state, exhibits a catalytic action in electroless plating. The amount of Pd adhered per unit area (including Pd ions and Pd metal) may be, for example, 1.7 μg / cm ² or more or 2.5 μg / cm ² or more.

Examples of the Pd compound include palladium chloride and the like. As the solvent used in the Pd compound solution, for example, hydrochloric acid or the like can be used. Specific examples of the Pd compound solution include 0.02% palladium chloride-0.01% hydrochloric acid aqueous solution (pH 3) and the like.

The contact temperature between the polyaniline layer and the Pd compound solution is not particularly limited and can be set appropriately, for example, 20 to 50 ° C. or 30 to 40 ° C., and the contact time is not particularly limited and can be set appropriately, for example. , 0.1-20 minutes, or 1-10 minutes.

[Step (D)]
In step (D), a metal layer is formed by performing electroless plating on the polyaniline layer on which the electroless plating catalyst is supported. By bringing the polyaniline layer on which the electroless plating catalyst is supported into contact with the electroless plating solution, a metal layer is formed as an electroless plating film on the polyaniline layer.

The metal type (plating metal) contained in the electroless plating solution is not particularly limited, and includes, for example, one or more metals selected from the group consisting of Cu, Ni, Au, Pd, Ag, Sn, Co and Pt. Can be done. In one embodiment, the electroless plating solution contains Cu. In addition to these, the electroless plating solution may contain elements such as phosphorus, boron, and iron.

The contact temperature between the polyaniline layer and the electroless plating solution can be appropriately set in consideration of the type of plating bath, the desired thickness of the metal layer, etc. For example, in the case of a low temperature bath, it is about 20 to 50 ° C. At high temperatures, it is 50 to 90 ° C.
The contact time between the polyaniline layer and the electroless plating solution can also be appropriately set in consideration of the type of plating bath, the desired thickness of the metal layer, and the like, and is, for example, 1 to 120 minutes.

The metal layer may be composed of only the electroless plating film formed as described above, or the metal layer may be provided with the same or different metal film by electroplating after the electroless plating film is provided. May be good.

Manufacturing example 1
[Manufacturing of polyaniline complex]
"Erosol OT" (sodium di-2-ethylhexyl sulfosuccinate) (AOT) 37.8 g and "Sorbon T-20" (manufactured by Toho Chemical Industry Co., Ltd.), which is a nonionic emulsifier having a polyoxyethylene sorbitan fatty acid ester structure 1 A solution of .47 g in 600 mL of toluene was placed in a 6 L separable flask under a nitrogen stream, and 22.2 g of aniline was further added to this solution. Then, 1800 mL of 1M phosphoric acid was added to the solution, and the temperature of the solution having two liquid phases of toluene and water was cooled to 5 ° C.

When the temperature inside the solution reached 5 ° C., stirring was performed at 390 rpm. A solution prepared by dissolving 65.7 g of ammonium persulfate in 600 mL of 1 M phosphoric acid was added dropwise over 2 hours using a dropping funnel. The reaction was carried out for 18 hours from the start of dropping while keeping the temperature inside the solution at 5 ° C. Then, the reaction temperature was raised to 40 ° C., and the reaction was continued for 1 hour. Then, it was allowed to stand and the toluene phase was separated. Toluene was added to the obtained toluene phase in an amount of 1500 mL, washed once with 500 mL of 1M phosphoric acid and three times with 500 mL of ion-exchanged water, the toluene phase was separated by allowing it to stand, and concentrated for concentration adjustment. 900 g of a toluene solution was obtained. The polyaniline complex concentration of this polyaniline complex toluene solution was 5.7% by mass.

The obtained polyaniline complex toluene solution was dried under reduced pressure in a hot water bath at 60 ° C. and dried to dryness to obtain 51.3 g of a polyaniline complex (powder).
The weight average molecular weight of the polyaniline molecule in this polyaniline complex was 72,000 g / mol, and the molecular weight distribution was 2.0.

Example 1
[Preparation of coating liquid 1]
27 g of propylene glycol monobutyl ether, 53 g of anon and 9 g of toluene were mixed to prepare a mixed solvent. To the mixed solvent, 1.2 g of polyester resin ("Byron GK810" manufactured by Toyo Boseki Co., Ltd.), 6 g of polyester urethane resin ("Byron UR1350" manufactured by Toyo Boseki Co., Ltd.), 1 g of curing agent ("JA-980" manufactured by Jujo Chemical Co., Ltd.) Was dissolved, 2.7 g of the polyaniline complex obtained in Production Example 1 was dissolved, and a resin modifier (“VD-3” manufactured by Shikoku Kasei Kogyo Co., Ltd.) was dispersed to obtain a coating liquid 1. .. The concentration of the polyaniline complex in the total solid content in the coating liquid 1 was 39%.

[Manufacturing and evaluation of circuit boards]
(Active energy ray irradiation process)
On the surface of the SPS resin molded sheet (“Zarek” (registered trademark) manufactured by Idemitsu Kosan Co., Ltd., dielectric loss tangent 0.005 (10 GHz)), which is the base material, an ultraviolet irradiation device (conveyor UV irradiation device manufactured by GS Yoursa Corporation). , Light source: metal halide lamp), and irradiated with ultraviolet rays, which are active energy rays, under the condition of 1000 mJ / cm ² .

(Formation of polyaniline layer (printing / coating process))
The coating liquid 1 was applied to the surface of the SPS resin film irradiated with ultraviolet rays using a bar coater (No. 16). The coating film was dried at 150 ° C. for 30 minutes and cured to obtain a polyaniline layer (electroless plating base film). Here, the coating amount of the coating liquid 1 was adjusted so that the film thickness of the polyaniline layer measured by the stylus type film thickness meter was 1 μm. The SPS resin molded sheet on which the polyaniline layer was formed was cut into 50 mm × 100 mm to obtain a test piece.

(Measurement of surface roughness Rz _JIS )
The surface roughness Rz _JIS of the surface of the polyaniline layer (the surface of the polyaniline layer opposite to the base material) in the obtained test piece was measured according to JIS B 0601: 2001. The measured values are shown in Table 1 as the surface roughness Rz _JIS of the metal layer formed on the polyaniline layer.

(Adhesion evaluation before plating)
The obtained test piece (for evaluation of adhesion) was subjected to an adhesion test in accordance with JIS K5600-5-6 (1999). The evaluation was performed according to the following criteria specified in JIS K5600-5-6, and classifications 0 and 1 were designated as "○" (pass), and classifications 2 to 5 were designated as "x" (fail). The results are shown in Table 1.
0: The edges of the cut are perfectly smooth and there is no peeling on any grid.
1: Small peeling of the coating film at the intersection of the cuts. The cross-cut portion is clearly not affected by more than 5%.
2: The coating film is peeled off along the edge of the cut and / or at the intersection. The cross-cut area is clearly affected by more than 5%, but not more than 15%.
3: The coating film is partially or wholly peeled off along the edges of the cut, and / or various parts of the eye are partially or wholly peeled off. The cross-cut portion is clearly affected by more than 15% but not more than 35%.
4: The coating film is partially or wholly peeled off along the edge of the cut, and / or some eyes are partially or wholly peeled off. The cross-cut portion is clearly not affected by more than 35%.
5: Any degree of peeling that cannot be classified even in classification 4.

(Degreasing process)
The test piece was immersed in a 2.5 mass% aqueous solution of a surfactant (“Ascreen” manufactured by Okuno Pharmaceutical Co., Ltd.) at 55 ° C. for 5 minutes. Then, the surface of the test piece was washed with running water and then immersed in a 10 mass% sodium hydrogen sulfite aqueous solution at 60 ° C. for 5 minutes. Further, the surface of the test piece was washed with running water and degreased.

(Catalyst support step)
The entire test piece after the degreasing treatment was immersed in a 20-fold diluted solution of a catalytic treatment agent activator (hydrochloric acid acidic Pd compound aqueous solution, manufactured by Okuno Pharmaceutical Co., Ltd.) at 30 ° C. for 5 minutes, and the metal Pd (metal Pd (metal Pd) was placed in the polyaniline layer. A treatment for supporting an electroless plating catalyst) was performed.

(Metal layer forming process)
The test piece after the catalyst-supporting treatment is plated with an electrolytic-free copper plating solution (“Sulcup ELC-SP” manufactured by Uemura Kogyo Co., Ltd.) at 60 ° C. for 60 minutes to perform an electrolytic-free copper plating layer (including copper). After forming the metal layer), it was washed with running water and dried with warm air (80 ° C.) to obtain a circuit board.

(Evaluation of adhesion after plating)
The obtained circuit board was subjected to an adhesion test by the same method as (adhesion evaluation before plating) and evaluated based on the criteria. In addition, this evaluation was performed only for those whose (adhesion evaluation before plating) was "○". The results are shown in Table 1.

Example 2
In Example 1, the same method as in Example 1 was used except that a polyimide film (“Kapton EN” manufactured by Toray DuPont Co., Ltd., dielectric loss tangent 0.0126 (10 GHz)) was used as the base material instead of the SPS resin film. The circuit board was manufactured and evaluated. The results are shown in Table 1.

Example 3
In Example 1, a circuit board was manufactured and evaluated by the same method as in Example 1 except that a liquid crystal polymer film (dielectric loss tangent 0.015 or less (10 GHz)) was used instead of the SPS resin film as the base material. The results are shown in Table 1.

Comparative Example 1
35 g of 3-methyl-3methoxybutanol, 5 g of butyl carbitol, and 10 g of petroleum naphtha were mixed to prepare a mixed solvent. To the mixed solvent, 30 g of urethane resin (“MAU1008” manufactured by Dainichiseika Kogyo Co., Ltd.), 6 g of urethane resin (“ASPU-360” manufactured by DIC Corporation), and epoxy resin (“HP-4710” manufactured by DIC Corporation) 0. 3 g and 0.3 g of a polyvinyl acetal resin (“KS-10” manufactured by Sekisui Resin Co., Ltd.) were dissolved, and 13.3 g of the polyaniline complex obtained in Production Example 1 was dissolved to obtain a coating liquid 2. The concentration of the polyaniline complex in the total solid content in the coating liquid 2 is 50% by mass.
In Example 1 (formation of polyaniline layer (printing / coating step)), the polyaniline layer having a thickness of 6 μm was formed by screen printing using the coating liquid 2 instead of the coating liquid 1, but the same as in Example 1. Circuit boards were manufactured and evaluated in the same way. The results are shown in Table 1.

Comparative Example 2
An attempt was made to manufacture a circuit board by the same method as in Example 1 except that the (active energy ray irradiation step) of Example 1 was not performed, but the adhesion before plating was "x" and (metal). In the layer forming step), the polyaniline layer was peeled off, and the circuit board could not be formed.

Example 4
(Preparation of copper-clad laminate film)
Coating liquid 1 is applied (bar coated) to one surface of an SPS resin film (thickness 50 μm, dielectric loss tangent 0.0004) that has been subjected to ultraviolet irradiation treatment on both sides using a bar coater (No. 8). , 150 ° C. for 10 minutes. Next, the coating liquid 1 was applied (bar coated) on the other surface of the SPS resin film using a bar coater (No. 8), and dried at 150 ° C. for 15 minutes. The thickness of the polyaniline layer (electroless plating base film) formed on both sides in this manner after drying was about 0.8 μm, respectively. The film thickness is a value measured by the same stylus type film thickness meter as in Example 1.
Both sides of the obtained test piece were subjected to a degreasing step, a catalyst supporting step and a metal layer forming step (electroless plating step) in the same manner as in Example 1, and a 1 μm thick electroless copper plating layer (metal containing copper) was subjected to. Layer) was formed. Next, using a copper sulfate bath, the film thickness (copper thickness) of the metal layer (copper layer) was increased to 12 μm by electroplating under the condition of a current density of 2 A / dm ² , to obtain a double-sided copper-clad film.

(Making microstrip lines)
A microstrip line and a ground (GND) terminal were formed on the obtained double-sided copper-clad film by the procedure described below.
First, a GND terminal for conducting the copper layers on the front and back surfaces of the double-sided copper-clad film was formed on the obtained double-sided copper-clad film by drilling and through-hole plating. The GND terminal is a microstrip line (width 140 μm, length 100 mm; the microstrip line is not formed at the stage of forming the GND terminal, but the formation position of the GND terminal will be described with reference to the formation position of the microstrip line. ), A total of four were formed so as to be arranged on both sides of the microstrip line in the width direction on one end side and the other end side in the longitudinal direction. With the above through-hole plating, the final copper thickness of each surface of the double-sided copper-clad film became 18 μm.
Next, the copper layer on one side (surface) of the double-sided copper-clad film was etched to form the microstrip line described above. On the other hand, the copper layer on the other side (back side) of the double-sided copper-clad film was not etched, and the entire surface of the copper layer was grounded (GND). In this way, a substrate for measuring transmission loss was obtained.
The surface roughness Rz _JIS of the SPS resin film (base film) side (corresponding to the polyaniline layer side) of the copper layer (metal layer) was 0.4 μm. The surface roughness Rz _JIS is a value measured as the surface roughness Rz _JIS of the surface of the polyaniline layer (the surface opposite to the base material in the polyaniline layer) by the same method as in Example 1.

(Transmission loss measurement)
The transmission loss of the obtained microstrip line of the substrate for measuring transmission loss was measured from the S parameter of 10 MHz to 110 GHz using a network analyzer “N5247” (Keysight Technology Co., Ltd.). The results are shown in Table 2.

Comparative Example 3
220 commercially available copper foils (JX Nippon Mining & Metals Co., Ltd., copper thickness 12 μm, Rz _JIS = 4.0 μm) are applied to both sides of an SPS resin film (thickness 50 μm, dielectric loss tangent 0.0004) that has been subjected to ultraviolet irradiation treatment on both sides. A double-sided copper-clad film was obtained by melt-pressing with a vacuum press device under heating at ° C. Similar to Example 4, a GND terminal was formed by drilling and through-hole plating, and a copper foil on one surface was etched to form a microstrip line to obtain a substrate for measuring transmission loss. Table 2 shows the results of measuring the transmission loss of the obtained transmission loss measurement substrate in the same manner as in Example 4.

Comparative Example 4
A commercially available double-sided copper-clad flexible substrate for high frequencies (base material: liquid crystal polymer 50 μm thickness, copper thickness 12 μm, Rz _JIS = 1.0 μm, relative permittivity 2.9 at 10 GHz, dielectric loss tangent 0.002) was prepared and used as an example. In the same manner as in No. 4, a GND terminal was formed by drilling and through-hole plating, and a copper foil on one surface was etched to form a microstrip line to obtain a substrate for measuring transmission loss. Table 2 shows the results of measuring the transmission loss of the obtained transmission loss measurement substrate in the same manner as in Example 4.

Comparative Example 5
A commercially available double-sided copper-clad flexible substrate for high frequencies (base material: polyimide 50 μm thickness, copper thickness 12 μm, Rz _JIS = 1.0 μm, relative permittivity 3.2 at 10 GHz, dielectric loss tangent 0.02) was prepared, and Example 4 Similarly, a GND terminal was formed by drilling and through-hole plating, and a copper foil on one surface was etched to form a microstrip line to obtain a substrate for measuring transmission loss. Table 2 shows the results of measuring the transmission loss of the obtained transmission loss measurement substrate in the same manner as in Example 4.

(Power attenuation)
There is the following relationship between transmission loss and power attenuation.
-6dB: Attenuated to about 1/4 as electric power -10dB: Attenuated to about 1/10 as electric power -20dB: Attenuated to about 1/100 as electric power Using the circuit board obtained in Example 4, millimeter waves or more It can be seen that the high frequency transmission loss can be significantly reduced.

The circuit board of the present invention can be used as a circuit board for in-vehicle radars, next-generation mobile phones, and the like.

Although some embodiments and / or embodiments of the present invention have been described above in detail, those skilled in the art will be able to demonstrate these embodiments and / or embodiments without substantial departure from the novel teachings and effects of the present invention. It is easy to make many changes to the examples. Therefore, many of these modifications are within the scope of the invention.
All the documents described in this specification and the contents of the application underlying the priority under the Paris Convention of the present application are incorporated.

Claims

With a resin base material having a dielectric loss tangent of 0.015 or less,
A polyaniline layer containing substituted or unsubstituted polyaniline,
The metal layer and the metal layer are laminated in this order and included.
The surface roughness Rz JIS of the surface on the polyaniline layer side of the metal layer is 0.5 μm or less.
Circuit board.
The circuit board according to claim 1, wherein the surface roughness Rz JIS of the surface of the metal layer on the polyaniline layer side is 0.25 μm or less.
The circuit board according to claim 1 or 2, wherein the polyaniline layer has a thickness of 5 μm or less.
The circuit board according to any one of claims 1 to 3, wherein the resin base material contains at least one selected from the group consisting of syndiotactic polystyrene, polyimide, liquid crystal polymer, polytetrafluoroethylene, and polyolefin.
The circuit board according to any one of claims 1 to 4, wherein the resin base material contains syndiotactic polystyrene.
The circuit board according to any one of claims 1 to 5, wherein the metal layer contains one or more metals selected from the group consisting of Cu, Ni, Au, Pd, Ag, Sn, Co and Pt.
The circuit board according to any one of claims 1 to 6, wherein the metal layer contains Cu.
The circuit board according to any one of claims 1 to 7, wherein the polyaniline layer contains a substituted or unsubstituted polyaniline as a polyaniline composite doped with a dopant.
The circuit board according to claim 8, wherein the dopant is an organic acid ion generated from a sulfosuccinic acid derivative represented by the following formula (III).

(In formula (III), M is a hydrogen atom, an organic radical or an inorganic radical. M'is a valence of M. R 13 and R 14 are independently hydrocarbon groups or-(, respectively. R 15 O) .R 15 is r -R 16 radicals are each independently a hydrocarbon group or a silylene group, R 16 is a hydrogen atom, a hydrocarbon group, or R 17 3 Si- groups, r is 1 These are the above integers. R 17 is an independent radical.)
The circuit board according to claim 8 or 9, wherein the dopant is sodium di-2-ethylhexyl sulfosuccinate.
The circuit board according to any one of claims 1 to 10, which is used for transmitting a high-frequency electric signal having a frequency of 1 GHz or more.
The method for manufacturing a circuit board according to any one of claims 1 to 11.
A step of applying one or more treatments selected from the group consisting of an active energy ray irradiation treatment, a corona treatment, and a frame treatment to the surface of the resin base material.
A step of forming the polyaniline layer on the surface of the resin base material subjected to the treatment, and
The step of supporting the electroless plating catalyst on the polyaniline layer and
A step of forming a metal layer by performing electroless plating on the polyaniline layer on which the electroless plating catalyst is supported is included.
How to manufacture a circuit board.
The method for manufacturing a circuit board according to claim 12, wherein the surface of the resin base material is subjected to an active energy ray irradiation treatment.
The method for manufacturing a circuit board according to claim 13, wherein the active energy ray is ultraviolet rays.
The method for manufacturing a circuit board according to claim 14, wherein the ultraviolet light source is a high-pressure mercury lamp or a metal halide lamp.
The method for producing a circuit board according to any one of claims 12 to 15, wherein the polyaniline layer is formed by a coating method using a composition containing a substituted or unsubstituted polyaniline.
The method for producing a circuit board according to claim 16, wherein the composition contains a substituted or unsubstituted polyaniline as a polyaniline composite doped with a dopant.
The method for manufacturing a circuit board according to claim 17, wherein the concentration of the polyaniline complex in the composition is 15% by mass or less.
The method for manufacturing a circuit board according to any one of claims 12 to 18, wherein the electroless plating catalyst is Pd.